Azo compounds



Patented July 9, 1940 zo COMPOUNDS James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N.- Y., a corporation of New Jersey Serial No. 176,890

No Drawing. Application November 27.1937,

16 Claims. -(01. 260-205) I This invention relates to aromatic azo dye compounds. More particularly, it relates to nuclear non-sulfonated aromatic azo dye compounds suitable for the coloration of organic de- 5 rivatives of cellulose. The invention includes the azo dye compounds, the process fortheir preparation, the process of coloring with them and materials colored with the azo dye compounds of the invention.

Organic derivatives of cellulose are characterized by an indifierent afiinity for the usual cotton or wool dyes, especially the ordinary watersoluble dyes. Typical organic derivatives of cellulose include the hydrolyzed as well as the unis hydrolyzed cellulose organic acid esters, such as cellulose acetate, cellulose iormate, cellulose propionate or cellulose butyrate, and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose, such as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellulose, ethyl cellulose or benzyl cellulose.

The aromatic azo dye compounds of our invention, broadly speaking, consist of azo compounds of a phenyl alkyl ketone, the phenyl nucleus of which contains two substituents selected from the group consisting of a. univalent aliphatic radical, 2. nitrogroup and a halogen atom.

These compounds may be prepared by diazotizing such a disubstituted phenyl alkyl ketoneamine 55 substituted phenyl alkyl ketones above defined,

they relate more particularly to the azodye compounds obtained by diazotizing a phenyl alkyl ketone amine having the formula:

45 wherein R represents an alkyl group and X and X1 each represent a univalent aliphatic radical such as an alkyl group-,an alko-Xy group or an alkcxyhydroxy group, a nitro group and a halogen atom such-as chlorine, bromine, fluorine or r50 iodine and coupling with an aryl; hydroaromatic or heterocyclic coupling component. Advantageously R is a methyl group.

The dye compounds obtained by the above de scribed coupling reaction may be'represented by the formula:

benzene or naphthalene series, a hydroaromatic coupling component such as 1,3-cyc1ohexadione or one derived from a 1,3-cyclohexadione, 5- methyl- ,1,3-cyclohexadione, 5,5-dimethyl-1,3-cyclohexadione and 5phenyl-1,3-cyclohexadione, 'for example, and a heterocyclic coupling component such a barbituric acid, thiobarbituric acid and compounds derived from these two substances, and a pyrazo-lone compound such as 1- phenyl-3-methyl-5 pyrazolone. Advantageously, R1 is an'aryl nucleus of the benzene series.

The nuclear non-sulfonated azo dye compounds of our invention constitute a valuable class of dyes suitable for the dyeing or coloration of material made of or containing an organic derivative of cellulose. The dyeings produced employing said non-sulfonated azo dye compounds are, in general, of good fastness: to light and washing and range in shade from yellow to purplish-blue. The nuclear sulfonated azo dye compounds of our inventiontpossess little or nopractical utility for the dyeing of organic derivatives ofv cellulose but may be used for the dyeing of such materials as cotton or wool, for example, being applied thereto by the customary methods of application. These nuclear sulfonated dye compounds may be prepared by sulfonation of the nuclear non-sulfonated com-1 PATENT. OFFICE j pounds in known fashion or by the use of suitable previously sulfonated substituents.

The following examples illustrate the preparation of the compounds of our invention:

zone are suspended in 200 cc. of water to which 30 cc. of 36% hydrochloric acid has been added. The resulting solution is cooled to a temperature approximating 0-5 C. and diazotized by adding,

with stirring, 6.9 grams of sodium nitrite dissolved in Water.

14 grams of 5,5-dimethyl-1,3-cyclohexadione are dissolved in 200 cc. of water containing 31.8 grams of sodium carbonate. The resulting solution is cooled to a temperature approximating 0-l0 C. and the diazo solution prepared as described above is slowly added with stirring. Upon completion of the coupling reaction which is carried out at a temperature of about O-10 C., the mixture is made acid to litmus by the addition of acetic acid follow ng which the dye compound is recovered by filtration, washed with water'and dried. The dye compound formed has the formula:

and colors cellulose acetate silk greenish-yellow from an aqueous suspension.

Example 2 tion, the mixture is allowed to stand for fifteen minutes and is then made neutral to Congo red paper by the addition of sodium acetate. Upon completion of the coupling reaction, the dye compound formed is precipitated by the addition of water, recovered by filtration, washed and dried.

The dye compound formed has the formula:

and colors cellulose acetate silk a red shade from an aqueous suspension.

Example 3 25.9 grams of 1-aceto-3-nitro-5-bromo-4- aminobenzene are added to 200 cc. of water to which 30 cc. of 36% hydrochloric acid has been added and the resulting mixture. is diazotized at a'temperature approximating 0-5 C. by the addition, with stirring, of 6.9 grams of sodium nitrite dissolved in water.

10.8 grams of p-cresol are dissolved in 100 cc. of water containing 10 grams of sodium hydroxide. The solution resulting is cooled-to a temperature approximating O-10 C. by the addition pound formedis recovered by filtration, washed with water and dried. It has the formula:

and colors cellulose acetate silk 2. yellow shade from an aqueous suspension.

Example 4 26.9 grams of di- -hydroxypropyl-u-naphthylamine are dissolved in 200 cc. of glacial acetic acid and the resulting solution is cooled to a temperature approximating 0-10" C. The diazo solution prepared in Example 3 is then added with stirring and a temperature of O-l0 C. is maintained throughout its addition. The mixture is then allowed to stand for 15 minutes following which it is made neutral to Congo red paper by the addition of sodium acetate. Upon completion of the coupling reaction, the dye compound formed is precipitated by the addition of water, recovered by filtration, washed with water and dried. The dye compound formed has the formula:

I /CH2OH2CH2OH W N: N

H O l CH2CH2CH2OH and colors cellulose acetate silk a wine color from an aqueous suspension.

Example 5 (A) 7.6 grams of powdered sodium nitrite are dissolved in 53 cc. (97.5 gm.) of cold concentrated sulfuric acid. After the addition, the solution is warmed to a. temperature not exceedng 70 C. following which it is cooled to a temperature of 10-15 C.

(B) 22.5 grams of 1 aceto 3,5-dinitro-4-aminobenzene are dissolved in 220 cc. of hot glacial acetic acid and following solution of the l-aceto- 3,5-dinitro-4-aminobenzene, the hot acetic acid solution is cooled rapidly to room temperature.

The mixture prepared in B is added to solution A over a period of 30 minutes while maintaining a temperature of 10-15 C. Following this addition, the resulting solution is stirred for one hour or more and then one gram of urea is added to remove any excess nitrous acid.

The diazo solution thus prepared is added with stirring to 20.9 grams of di-y-hYdIOXYMDPYl aniline dissolved in cc. of glacial acetic acid. This addition is effected while maintaining a temperature approximating 010 C. The mixture is then allowed -to stand for 15 minutes following which it is made neutral to Congo red paper by the addition of sodium acetate. Upon completion of the coupling reaction which takes place, the dye compound formed is precipitated by the addition of Water, recovered by filtration, washed and dried. The dye compound formed in the example has the formula:

| /CH2CH2CH2OH O CHzCHgCHzOH and colors cellulose acetate silk red from an aqueous suspension.

Example 6' O C'HaGHzOH and colors cellulose acetate silk wine from an aqueous suspension.

Ezample 7 13.7 grams of p-hydroxyethylaniline are dissolved in 100 cc. of glacial acetic acid and the resulting solution is cooled to a temperature approximating -10 C. The diazo solution prepared in Example is then added, with stirring, while maintaining a temperature of about 0-l0 0. Following its addition, the mixture is allowed to stand for one hour after which it is made neutral to Congo red paper by the addition of sodium acetate. Upon completion of the coupling reaction, the dye compound formed is precipitated with water, recovered by filtration, washed with water and dried. The dye compound formed has the formula:

No, and colors'cellulose acetate silk red from an aqueous suspension.

J Example 8 25.8 grams of ethyl-3-methoxy-5-bromo-4-amino-phenyl ketone.

- Br l are diazotized in the usual manner and coupled with 17.7 grams of B-hydroxyethylcresidine dissolved in cold dilute hydrochloric acid. The coupling is completed by adding sodium carbonate following which the dye compound is recovered by filtration, washed with water and dried. The

dye compound formed has the formula:

and colors cellulose acetate silk red from an aqueous suspension. 7

The following tabulation further illustrates the compounds included within the scope of our invention together with the color they produce on cellulose acetate silk. The compounds indicated below may be prepared by diazotizing the amine listed under the heading Amine and. coupling with the compound specified in the column entitled Coupling component. tization and coupling reactions may, for example, be carried out following the general procedure described in Examples 1 to 8 inclusive.

The diazo- Amine Couphng component g gg g gi l-aceto-3,5 diiodo-4-aminobenzene Barbitul'ic acid Greenish-yellow. 1-aceto-3-bromo-5-nitro-4-anfinobenzene .d0 Do. 1-acet0-3,5-dinitro-4-aminobenzene J1 Do. 1-aCeto-3,5-diiodo-4-aminobenzene 5,5-dimethyl-l,3-cyclohexad1one Do.

. 1-acet0-3-b1'omo-5-nitro-4-aminobenzene. do Do. l-aceto-3,5-dinitro-4-aminobenzene Do. l-aceto-3,5-diiodo-4-aminobenzene Yellow. l-aceto-3-bromo-5nitro-4-aminobenzene Do. l-aceto-3,5-dinitro-4-aminobenzene. Do. l-aeetoB,5-diiodo-4-aminobenzene Orange yellow. l-aceto-3-bromo5-nitro-4-aminobenzene Do. l-aceto-S,5-dinitro-4-aminobenzene Orange. l-aceto-B,5-diiodo-4-aminobenzene. Orange-yellow. l-aceto-3-bromo-5-nitro-4-aminobenzen Orange. l-aceto-3,5-dinitro-4-aminobenzene. Orange red. l-acet0-3,5diiodo-4-aminobenzene. Red. 1-aceto-3-bromo-5-nitro-4-aminobenzene D0. l-aceto-B,5-dinitro-4-aminobenzene. Do. l-aceto-3,5-diiodo-4-aminobenzene Do. l-acet0-3-bromo-5-nitro-4'aminobenzene Do. l-acet0-3,5-dinitro-4-aminobenzene do Do. l-aceto-3, 5-diiodo-4-aminobenzene Di-'y-hydroxypropyl-a-naphthylamine Do. l-aceto-3'bromo-5-nitro-4-aminobenzene d0 Purplish red. 1-aceto-3, 5-dinitro-4-aminobenzene do Violet. l-acetor3, 5-diiodo-4-aminobenzene m-Methoxy-di-fl-hydroxyethylaniline Red. l-aceto-3-bromo-5-nitro-4-aminobenzene do Do. 1-aceto-3, 5-dinitro-4-aminobeuzene do Do.

H 1-aceto-3, 5-diiodo-4-aminobenzene %G-GHB Do.

H l-aceto-3-bromo-5-nitro-4-aminobenzene %-CCH5 D0.

l-aceto-3, 5-dinitro-4-aminobenzene do Do. l-aceto-3, fi-diiodol-aminobenzene Ethyl-fi-hydroxy ethyl cresidine.. Do. l-aceto-3-bromo-5-nitro-4-aminoh nmm Do. 1-aceto-3, 6-dinitr0-4-a.min0benzen do Do.

- Color on cellulose Amine Coupling component acetate Silk 1-aeeto-3, 5-diiodo-4-aminobenzene B-hydrOxy ethyl-m-toluidine Red.

1-acet0-3-bron1o-5-nitro-4-aminobenzenel Do.

1-aceto-3, -dinitro4-aminoben mm 13 Ethy1-3-methy1-5-nitro-4-amino-phenyl ketone. Do.

l-aceto-3-chloros5-nitro-4-aminobenzene -1-amino-5-napht1101 Blue.

Ethyl-3, 5-dichloro-4-amino-phenyl ketone Di-fi-hydroxyethyl-amlme- Orange Ethyl-3, fi-dim'troi-amino-phenyl ketone do Red.

Ethyl-3-chloro-5-methyl-4-am.inopheny1 ketona. -do Orange.

Eiiliyl 3 methoxy 5 chloro 4 aminophenyl Ethyl-B-hydroxyethyla Do.

etone.

Ethyl-3-metboxy-5-nitro-4-aminophenyl ketonedo Red.

Ethyl-3, 5-din1ethyl-4-an1inophenyl ketone 1-amino-2-methoxy-fi-methylbenzene Yellowish-orange.

Ethyl-3, 5-dimethoxy-4-aminopheny1 ketone fl-hydroxyethylanilinen Do.

l-aceto-3, 5-dimethoxy-4-aminophenyl kotone- Do.

l-aceto-B, 5-dimethyl-4-aminophenyl ket0ne Do.

1-aceto-3-methyl-5-chloro4-aminophenyl keton Green-yellow. l -kacet0 3 methyl 5 chloro 4 aminophenyl Ethyl-B-hydroxyethylaniline Orange.

etone.

In order that our invention may be fully understood, the preparation of a number of intermediate substances employed in the manufacture of the dye compounds of our invention is disclosed hereinafter.

Compounds having the general formula:

" wherein X and X1 each represents a halogen page 158 (1928).

atom may be prepared by halogenation of methyl-3-chloro-4-aminophenylketone, methyl- 3-bromo-4-aminophenylketone or methyl-3-iodo- 4-aminophenylketone, for example. The preparation of these latter named compounds is indicated herein.

Preparation of methyl-3-chloro-4-aminophenyl Icetone This compound may be prepared as described in Journal of the Chemical Society, volume 85, pages 340-341 (1904).

Preparation of methyl-3-bromo-4-aminophenyl ketone Preparation of methyl-3-iodo-4-aminophenyl ketone This compound may be obtained by preparing para iodo acetanilide as described in Journal of the Chemical Socity, vol. 105, page 125 (1914), and converting it to the desired product by treatment with hot aqueous hydrochloric acid.

Compounds having the general formula:

X1 CEMHJQNEB wherein X represents a nitro group and X1 represents a halogen atom may be prepared by halogenation of methyl-3-nitro-4-aminophenylketone which can be prepared as described in Journal of the Chemical Society, page 2403, for the year 1931.

Preparation of methyl-3,5-dinitro-4-aminophenylketone (1 -aceto-3,5-dinitro-4-aminobeneene) This compound can be prepared as described in Recueil Travaux Chimique Pays Bas, vol. 34, page 208 (1915).

Preparation of ethyl-3,5-dinitro-4-aminopheny ketone This compound can be prepared by the method described in Recueil Travaux Chimique Pays Bas, vol. 34, page 208 (1915).

Preparation of ethyl-1-chZoro-5methyZ-4- aminophenyllcetone This compound can be prepared by the method described in Journal of the Chemical Society, vol. 85, pages 340-341 (1904).

Preparation of methyl-3,5-dimethyl-4-aminophenyllcetone (1 -aceto-3,5 -dirnethyZ-4-amin0=- benzene) This compound may be prepared by the general method of Kunckell Berichte der deutschen 1 cooling is recovered by filtration. This solid material is By treatment of it with hydrochloric acid, methyl-3,5-dimethyl-4-aminophenylketone can be obtained in its free amine form.

Preparation of methyl-3,5-dimethoa:y-4-aminophenyllcetone (1-aceto--3,5-dimethoa:y 4 aminobenzene) This compound may be prepared by the same general method described above in connection with the preparation of methyl-3,5-dimethyl-4- aminophenylketone.

In order that the application of the compounds of our invention may be clearly understood their application for the direct dyeing or coloration of materials made of or containing an organic derivative of cellulose, and more particularly cellulose acetate silk, is described hereinafter. Although the remarks are more particularly directed to the dyeing or coloring of the above mentioned materials thosepertaining to temperature, the dispersing agents and the amounts of dispersing agent and dye which may be employed, for example, are of general applicability where the dye is to be applied directly to the fiber from an aqueous suspension. The general methods by which the dye compounds may be applied to the coloration of other materials are well known in the art and need not be described here. a I

In employing the aromatic azo derivatives of our invention as dyes, they will ordinarily be applied to the material in the form of an aqueous suspension which canbe prepared by grinding the dye to a paste in the presence of a sulfonated oil, soap, or other suitable dispersing agent and dispersing the resulting paste in water. Dyeing operations can, with advantage, be conducted at a temperature of 85 C.,- but any suitable temperature may be used. In accordance with the usual dyeing practice, the material to be dyed will ordinarily be added to the aqueous dye bath at a temperature lower than that at which the main portion of the dyeing is to be effected, a temperature approximating 45-55" C., for example, following which the temperature of the dye bath will be raised to that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted will vary somewhat, depending, for example, on the particularmaterial or materials undergoing colorations.

The amount of dispersing agent employed may be varied over wide limits. Amounts approximating 10 to 200% by weight on the dye may be employed, for example. These amounts are not to be taken as limits as greater or lesser amounts can be used. To illustrate, if the dye is ground to a sufficiently fine powder, dyeing can be satisfactorily carried out without the aid of a dispersing agent. Generally speaking, however, the use of a dispersing agent is desirable.

Advantageously, dyeing is carried out in a substantially neutral dyebath. Perhaps, more accurately, it should be stated that dyeing should not be carried out in an alkaline dyebath, that is, one having any substantial alkalinity, since the presence of free alkali appears to affect the dyeing adversely. Dyeing in an acid dyebath is not recommended because of the tendency of acids to affect the material undergoing dyeing adversely. Because of these considerations when a dispersing agent is to be employed preferably it is neutral or substantially neutral.

It will be understood that the azo compounds of our invention may be applied to the material to be colored in any suitable manner. Coloration may be effected, for example, by dyeing, printing, or stenciling. Dispersing or solubilizing agents that can be employed for preparing suspensions of the dye include soap, sulphoricinoleic acid, salts of sulphoricinoleic acid, a water soluble salt of cellulose phthalate, cellulose succinate or cellulose mono-acetate diphthalate, for example, the sodium, potassium or ammonium salts, and sulfonated oleic, stearic or palmitic acid, or salts thereof, such, for example, as the sodium or ammonium salts.

While it is preferred to efiect coloration by applying the dye compound from anaqueous dyebath directly tothe material to be.co lored,.the azo compounds of our inventionmay be applied employing the methods applicable tothe so-called ice colors. Briefly, in accordance with this method of dyeing, the amine is absorbed and diazotized on the fiber after which the dye is formed in situ by developing with a coupling component such as 5-methyl-1,3-cyclohexadione or .ethyl-,8-hyclroxyethylaniline,' for example. Conversely, the material undergoing dyeing or coloration may first be treated to absorb one of, said coupling components and the dye subsequently formed in situ by coupling with a diazonium salt of the benzene or naphthalene series.

The following examples illustrate how dyeing may be carried out in accordance with our invention. Quantities are expressed in parts by weight.

Example A 2.5 partsof /CH2CH2CH2OH O I CH2CH2CH2OH N02 are finely ground with a dispersing agent such as soap or oleyl glyceryl sulfate and the resulting paste is dispersed in 1000 parts of water. The dispersion thus prepared is heated to a temperature approximating 45-55 C. and parts of cellulose acetate silk in the form of yarn or fabric, for example, are added to the dyebath after 7 Example B By the substitution of 2.5 parts of I Y O com cm H for dye compound of Example A, cellulose acetate silk can likewise be dyed a reddish shade of excellent light fastness in an exactly similar manner as described in said example.

While our invention has been illustrated in connection with the dyeing of cellulose acetate silk, it will be understood thatdyeing operations can be carried out in a manner similar to that described above by the substitution of another CHLOE organic derivative of cellulose material for celluloseacetate silk or by employing dye compounds other than those employed in the examples or by substitution of both the material being dyed and the dye compounds of the examples.

We claim:

1. An azo dye having the general formula:

wherein R represents the residue of a phenylalkyl ketone, the phenyl nucleus of which contains two substituents selected from the group consisting of a univalent aliphatic radical, a nitro group and a'halogen atom and wherein R1 represents a member selected from the group consisting of an aryl nucleus of the benzene and naphthalene series, a hydroaromatic nucleus and a heterocyclic nucleus.

2. An azo dye having the general formula:

wherein R represents the residue of a phenylalkyl ketone, the phenyl nucleus of which contains two substituents selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and wherein R1 represents an aryl nucleus of the benzene series. 3. An azo dye having the general formula:

where R represents an alkyl group, X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a member selected from the group consisting of an aryl group of the benzene and naphthalene series, a hydroaromatic nucleus and a heterocyclic nucleus.

4. An azo dye having the general formula:

leagues wherein R represents an alkyl group, X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents an aryl nucleus of the benzene series.

6. An azo dye having the general formula:

wherein R represents an alkyl group, X and X1 each represent a member selected from the group consisting of -a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents an aryl nucleus of the benzene series.

'7. An azo dye having the general formula:

wherein R represents an alkyl group, X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a nuclear non-sulfonated aryl nucleus of the benzene series.

8. An azo dye having the general formula:

WhereinXand X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents an aryl nucleus of the benzene series.

9. The azo compound having the formula:

N02 /C1Hs 10. The azo compound having the formula:

N O 1 C H3 11. The azo compound having the formula:

12. Material made of or containing an organic derivative of cellulose colored with a dye, having afiinity for organic derivatives of cellulose, selected from the class of azo compounds having the general formula:

wherein R represents an alkyl group, X and X1 each represent a, member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a nuclear non-sulfonated member selected from the group consisting of an aryl group of the benzene and naphthalene series, a hydroaromatic nucleus and a heterocyclic nucleus.

13. Material made of or containing an organic acid ester of cellulose colored with a dye, having aflinity for organic acid esters of cellulose, selected from the class of azo compounds having the general formula:

wherein R represents an alkyl group, X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a nuclear non-sulfonated member selected from the group consisting of an aryl group of the benzene and naphthalene series, a hydroaromatic nucleus and a heterocyclic nucleus.

14. A cellulose acetate colored with a dye, having affinity for cellulose acetate, selected from the class of azo compounds having the general formula:

wherein R represents an alkyl group, X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a nuclear non-sulfonated member selected from the group consisting of an aryl group of the benzene and naphthalene series, a hydroaromatic nucleus and a heterocyclic nucleus.

15. A cellulose acetate colored with a dye, having affinity for cellulose acetate, selected from the class of azo compounds having the general formula:

wherein R represents an alkyl group, X and X1 ing affinity for cellulose acetate, selected from the class of azo compounds having the general formula:

wherein X and X1 each represent a member selected from the group consisting of a univalent aliphatic radical, a nitro group and a halogen atom and R1 represents a nuclear non-sulfonated aryl nucleus of the benzene series.

JAMES G. McNALLY. JOSEPH DICKEY. 

